Isophorone imines



Patented Dec. 26, 1950 rsornononn IMINES Vernon E. Haury, El Cerrito,and Seaver A. Bailard, Orinda, Calif., assignors to Shell DevelopmentCompany, San Francisco, Calif., a corporation of Delaware No Drawing.Application December 19, 1946,

Serial No. 717,322

This invention relates to a novel class of ketimmes having especiallyadvantageous properties. It deals particularly with new unsaturatedisophorylidene ketimines which are useful components of insecticidalpreparations and with an eificient and economical method for producingsuch ketimines.

The ketimines of the invention are characterized by an imine nitrogenatom which is linked by a double bond to an isophorylidene radical, i.e. a 3,5,5-trimethyl-A -cyclohexenylidene radica The imine nitrogen atomin the new compounds is also directly linked bya single bond to anunsaturated aliphatic or alicyclic hydrocarbon radical having a doublebond between two carbon atoms, one of which is preferably directlyattached to the carbonatom which is directly linked to the iminenitrogen atom. The preferred isophorylidene ketimines of the inventioncontain ellelven to about twenty carbon atoms per molec e.

These new ketimines have unexpectedly valuable properties due to theirunique structure, particularly the characteristic arrangement of thethree methyl groups and the olefmic double bond in the isophorylideneradical and the unsaturated nature of the other radical attached to theimine nitrogen atom. These structural features give the new compoundsmany industrially important applications in which previous ketimines areunsuitable Or much less desirable. The new ketimines may, for instance,be used in insecticidal compositions where they are unusually irritatingto insects, particularly flies, and cause a violent paralysis. They mayalso be used as compounding agents for rubber, and as intermediates inthe synthesis of other types of valuable organic compounds. They areuseful in the preparation of corrosion inhibitors for lubricating oilsand in the synthesis of improved wetting agents, and may be used asstarting materials for the production of secondary amines. Due to theirunsaturated character they may be copolymerized with polymerizableunsaturated compounds such as vinyl chloride, methyl methacrylate,diallyl phthalate, butadiene, etc., to produce valuable plastics andresins. prejferred 9 Claims. (Cl. 260-566) subgroup of the novelketimines which are especially useful in such applications are thosehaving an unsaturated terminal carbon atom, most preferably anunsaturated terminal carbon atom in a chain of not more than threecarbon atoms directly attached to the imine nitrogen atom.

The imines of the present invention may be readily and economicallyprepared in high yields by reacting a primary aliphatic or alicyclic unsaturated amine, perferably having two to about twelve carbon atoms permolecule, with isophorone in the absence of a catalyst for condensationreactions. Most preferably the reaction is carried out under conditionswhich will favor or promote the elimination of water from the reactionmixture substantially as soon as it is formed therein. This object maybe realized in a variety of different manners. It has been foundespecially efficient and desirable to carry out the reaction in adehydrating still at about the boiling temperature of the reactants. Bymaintaining a heavy reflux in the column it is possible to withdraw thewater from the reaction mixture substantia ly as soon as it is formed.When all of the water has been thus removed, the product may befractionally distilled, thereby separating the imine from any unreactedamine or isophorone as well as from any lay-products which may have beenformed during the course of the reaction. This method of operation is aparticularly rapid one, since in most cases the reac-] tion may becompletely carried out over a period of only from about one hour toaboutfive hours. The rapidity of the present process does not; moreover, cutdown the yield of product or result in the formation of an impureproduct since,

as will be shown more fully hereinbelow, high yields of pure imine maybe obtained.

If necessary or desirable because of the nature-- nature of the imine issuch that it forms an azeotropic mixture with water or withotherconstituents of the reaction mixture, the azeotropic mixture maybedistilled over from the reaction vessel and the desired iminesubsequently sepa: rated therefrom. This may be done by an) suite ablemeans, as by stratification, fractionation,

extraction, salting out, use of drying agents, and

the like. The imine may, if desired, be further Purified or isolated ina pure state by subjecting Thus, all or part of the imine '3 thecondensate to treatment in suitable fractionation equipment.

It may in some instances be desirable to carry out the reaction in thepresence of an inert solvent in order to better control the reaction andto facilitate the removal of the water formed dur' ing the course of thereaction. Suitable substances for this purpose include any inertmaterials having a suitable boiling point which will:

act as mutual solvents for the reactants without entering into chemicalcombination therewith. Certain alcohols, esters, ethers, hydrocarbonsespecially the aromatic hydrocarbons such astoluene, the xylenes, andthe-.like-exempliiy suit-- able solvents to be used for this purpose.

The process of the invention, may be executed in a batch, intermittentor continuous manner.v When it is desired to execute the process in acontinuous manner, a suitable reaction stage-- or. stages incommunication with one or a plurality of separation! and purificationstages may.- be provided. The volume of.- the reaction mixture. and: therelative concentrations of thereactants inrthe reactionstage or,stagesmay be keptsubstantially constant byv the intermittent: or con.-tinuous, introduction therein of the reactants at about the same rateat.which they are: reacted and the products, removed fromthe-reactionmixture. The reactants separated from the condenseddistillate may bare-utilized by introduceing; them into al reaction.stageas a. mixture-i1 dependently or, in: com unction. with 1 the 1main. reactant; feed or feeds.

As an alternative mode-of operation the condensation. may be effectedina reaction. column intowhich the 1 reactants may beintroduced at oneora; plurality of zones, thelooation of which zones is dependent upon therelative I boiling-,temperatures of the particular reactants, products,

and constant boiling mixtures: which. may be for-med;

Iminesw may be prepared, in, accordance with the process disclosedherein byreacting asingle unsaturated amine with isophorone, thusformingpasingle imine asa product.v However, if it. isv desired.toprepare a", mixture of imines; this may be accomplished by; reacting.-a: mixtureof dilferent species of unsaturated amines with isophorone.-The-resultingmixture oi -imines: may be used. without resorting toseparation of the constituents; or, if desired, separation of the iminesmay be effected by anyg suitablemeans; asby. fractional distillation, i1there-eis a. sufiiciently great difference; in, theboiling temperatures;of; the imines:

In; the: majority of: cases, they: condensationi is:

effectedby heating the" reactants inicontacfiwith' each other atthe;boili 1igtemperature:Offtheme action;mixture:under atmosphericpressure:- Superatmospheric pressuresamay be-used if: desired; however,as where; it is: expedient to accelerate the-rate,of-the'reaction-byincreasing thetemperaturei at which it i is carriedout; Similarly, itgmay, be advantageous; to use subatmospherictemperatures in certain. cases, as l Where; boilingofv the reaction.mixture and distillation of,- the productcannotbe efiected' atatmosphericv pressure. without.- decomposition, of; the; reactants; or.of, the product.

In. theordinary case; ,sufiiciently intimate goon-- tact, is maintainedbetween, the constituents of, the reaction mixture by:theebullition ofthe con tents of, the. reaction vessel. However; othermeans such asstirring, shaking, etc;. may be, ree sortedtojf desirable in a givencase; A

iii)

A variety of primary unsaturated amines may be used as startingmaterials for the synthesis of imines by the process of the invention.These include those non-aromatic unsaturated amines which are members ofthe olefinic and cyclo-olefinichomologous series, 1. e. those in whichthe iniino groups are attached to a radical. selected from the groupconsisting of the alkenyl and cyclo-alkenyl radicals. Diamines may beused as well as the mono-substituted compounds. Certain of thenon-aromatic heterocyclic amines may also be used, e. g. those in whichthe hetero atom is oxygen, sulfur or nitrogen. Functional groupsother'than the amino groups may also be present intheimoleculeiof thestarting unsaturated amine provided these are of such a nature as to benonreacting under the conditions of the reaction so as not to formundesirable by-products. Such functionali groups include, for example,the halogen, hydroxyl and ether groups. Specific examples-ot primaryunsaturated amines whichmay be; used in the synthesis,v therefore, are:vinylamine allylamine, methallylamine, crotylamine, isocrotylamine,isopropenylamine', leamino i propene, l-amino-l-butene,I-amino-B-butene, Z-amino-l-butene, Z-amino-tZ-butene, 2-amino3--butene, l-amino-Z-pentene, 3-amino-l-pentene, 3,-amino-2emethylelbutene,Z-amino-l-hexene, 2rmethyl-2-amino-4-pentene, 4-amino-4-octene,3e-methyll-3 aminorl-heptene, l-amino-Z-decene, IraminQ-Z-undecene,lramino-2-dodecene, oleyl' amine, and like aliphatic unsaturated amines,and aminocyclopentene-l, aminocylopentene-Z, aminocyclopentene-3, theaminocyclohexenes, lmethyl 1 aminocyclopentene 2, 1-methyl-2-aminocyclopentene-l, l-metliyl- 2 aminocyclopentene-5,1-metl'iyl-3eaminocyclohexene-1, 1- methyl-4-amihocyclohexene-Z,l-ethyl-l-aminocyc1ohexene-2, 1,1 dimethyl-2-aminocyclohexene-Z1,1edimethyl-5-aminocyclohexene3,, 1,3? dimethyl-5raminocyclohexene-ii,1,1;3-trimethyla 5L-aminocyclohexene3 and similar alicyclic unsaturated.amines.

As willlbe apparent froman inspection of the equation. representing the.condensation, between theiprimary unsaturated, amineand isophorone inaccordance, with the present invention CH2. CHrt l CHs oHi=ocycloaliphatic' radical), one 7 mol? or equivalent weight. of: primaryunsaturated amine should; theoretically, .be used for: each mol orequivalent weight? of isophorone. However; since the'reaction is' anequilibrium reaction, the equilibrium may 'be shifted and the"production :of theldesired imine 1 favoredi by theuse of an excess ofone of the: reactants; An excess: of eitherthe primary amine or; ofisophorone maybe used; depending upon: which one isv the more: readily:available,- which may be more readily; separated from the product, andother considerations of av practical, Usually it. is preferredr touse anex nature @555. the; isophorone: since: it: is" often the" more readilyavailable and since in most cases the excess isophorone may bethoroughly and easily separated from the imine product. The amount inexcess of the theoretical which may be used may vary with eachparticular preparation, although it has been found that, in general, aratio of one equivalent of unsaturated amineto from about 1.25 to about2.0 mols of isophorone is a preferred ratio.

The following examples in which the amounts are given in parts by weightillustrated one advantageous method of preparing the new unsaturatedisophorylidene ketimines of the invention,

Example I A mixture of two mols of isophorone, two mols ofmethallylamine, 200 cc. of benzene and 2 grams of zinc chloride isheated under a dehydration column with continuous removal of the waterformed in the reaction. After about 4 hours of distillation thetheoretical amount of water is removed and the remaining mixture isfractionated at 1-2 mm. pressure with the following results:

Boiling Range of Fraction, C. Grams 51-61 at 1-2 mm 32 (ii-73 at 1-2 mm31 7376 at 1-2 mm 219 76-82 at 1*2 mm 45 Bottoms. 38

The material boiling between 73 C. and 76 C. at 1-2 mm. is N-methallylisophoronimine having an index of refraction 11 1.5020 and analyzing7.05%-7.06% nitrogen. Yield, about 57.4% of the theoretical based on thestarting isophorone or methallylamine.

Example II Isophorone (2 mols), allylamine (2.35 mols), zinc chloride (3grams), benzene (100 cc.) and petroleum ether (50 cc.) are heatedtogether under a column having a phase separating head with constantremoval of the water formed. After about 13 hours the removal of waterappears to be complete and the catalyst is destroyed with sodiumhydroxide. Distillation gives 132 grams of unreacted isophorone and 89grams of N-allylisophoronimine boiling at 104 C.104.5 C. under 10 mm.and having a refractive index n 1.5050, a conversion of about 25% with a48% yield.

Example III l-vinylpentane) isophoronimine from 3-methyl-3-amino-1-heptene. Especially good yields are obtained when reactingisophorone with isophorylamine under the conditions of Example II,

the product being N-isophorylisophoronimine Under the same conditionsN-(2-cyclopentenyl) isophoronimine is obtained when usingaminocyclopentene-2 in place of isophorylamin-e and N-(3 methyl 2cyclohexene) isophoronimine when using l-methyl-l-aminocyclohexene-Q asthe amine.

, As previously pointed out, the new unsaturated aliphatic and alicyclicisophoronimines of the inyention are particularly useful as insecticidesor components of insecticidal mixtures. The preferred isophoroniminesfor use as insecticides are those having attached by a single bond tothe imino nitrogen atom a hydrocarbon radical containing one, and onlyone, pair of doubly bonded carbon atoms. Those having 11 to about 15carbon atoms are especially suitable for this application. They may beapplied, either alone or in combination with other active or inactivesubstances, to plants, animals, fabrics and the like by spraying,dusting, dipping, etc., in the form of concentrated liquids, solutions,suspensions, dusting powders or other suitable ways. They are, forinstance, advantageously used in the form of dilute solutions insolvents such as petroleum distillate, lignite tar oils, paraffin oils,naphthenes, chlorinated hydrocarbons such as dichloropropane,chlorinated ethers, ketones such as acetone, monoand poly-hydricalcohols including fenchyl and bornyl alcohols for example, glycolethers, or other solvents or mixtures thereof.

I Foruse in household insecticides, where they are especiallyadvantageous because they combine high effectiveness on insects with lowtoxicity to. man and other warm-blooded animals, the new unsaturatedisophoronimines are preferably dissolved in a light hydrocarbon oil suchas highly refined, odorless kerosene with or without other insecticides.Ordinarily, from about 1% to 20%, preferably from 2% to 8%, of the newisophoronimines are used in such sprays. Solutions of the new N-alkenyland N-cyclo-olefinic isophoronimines in odorless kerosene distillate,for instance, when placed on filter paper and exposed to the air, leaveno stain after evaporation of the liquid -a feature of particularadvantage in household insecticides.

For use in sprays, such, for instance, as horticultural sprays,emulsions of the N-alkenyl isophoronimine and N-cyclo-olefinicisophoronimines prepared with emulsifying agents such as partial estersor polyhydric alcohols e.g. glycerol mono-oleate, polyethylene glycollaurate or stearate, etc., or various soaps, or alkali metal salts ofsulfuric acid monoesters or of organic sulfonic acids, or the like, maybe advantageously used.

Among the other insecticides or fungicides with which the new compoundsof the invention may be used with advantage are, for instance,pyrethrum, derris resins, rotenone, nicotine, limesulfur, Bordeauxmixture, copper sulfate or carbonate, sulfur, mercury compounds,arsenates, phenol, paradichlorobenzene, thiocyanates, isothiocyanates,unsaturated chlorides, unsaturated Percent :Pcrcent. 1111mm, 101111114110111.

; knock km down N-methallylisophoronimine 100' 5GN-ezllylisophoronimiimam- 68- i 19 N-isobutylisophoronimine 36 r 23 Nmethallylacetylisophoronimine; j 10 Besides the control of. hous'eflies(Mus'cw' dcm'estica) compositions comprising" a? carrier and an 1Nalkenyl or N cyolo-olefinic isophoronitnine may. be use'd'gin theeradication or control of. variousother peStS,, including, insectssuchyfor example, aslaphids; diabrotica', red spiders; thrips'; etci,or" bacteri'axand fungi", such as Aspergillus; Penicillium; Sche'wb'iumrolsz'i; and" the like.

This application, is a continuation-in-part of our: copendingapplication, Serial; No; 512,042, me iNovemberiz'l, 1943; now abandoned.

We claim astour invention I; Imines o'i the general formula (2H3;(JH'a-(L -CHQ on;

CH==G where n is an integere'qual to" atle'ast z'ldut not greaterthan 18and dis an'odd integer not greater than 3,1 the CnH m-a group.containing not more 45 than one" pair of' doubly bonded carbon atoms:

' alkylcycloalkenyl radical a tertiary olefinic carbon atom which isdirectly linked to the carbon atom directlyattached to" the imine;nitrogen atom.

82 N- (trimethylcyclohexenyll isophoroniinines wherein the methyl groupsare attached" to the No: 3 and'N'o: Scarbon-atomsof the cycloliexenylring."

9. Niso'phoryl"isophoronimine.

VERNON E. HAURSL SEAVER A. BALLARD.

REFERENCES CITED.

The following references are of recordin the file of this patent:

UNITED STATES-PATENTS Number Name Date Re. 22,524 Ballard et al. Aug. 1,1944 2,045,574 Adkins V June30, 1936. 2,057,044 Meisenburg Oct; 13, 19362,207,721 Coleman Juli! 16, 1940 2,217,622 Lichty Oct. 8, 1940 2,218,587Reddelin Oct. 22, 1940 2,381,526 Throdahl Aug. 7, 1945 2,394,280Williams Feb. 5, 1946 2,425,185 Haury Aug. 5, 1947 FOREIGN PATENTSNumber: Country. Date 360,221 Germany Sept; 30, 1922] 527,267" GermanyJune15, 1931

1. IMINES OF THE GENERAL FORMULA